Bismuth(III) complexes with sulfur and selenium donor ligands: synthesis and crystal structures of BiCl3·Prn2P(S)P(S)Prn2 and [(Me2N)3PSeSeP(NMe2)3]2+[(BiCl4)2]n2n–
Direct addition of bismuth(III) chloride and tetra-n-propyldiphosphane disulfide gave bright yellow crystals of the 1 : 1 adduct BiCl3·Prn2P(S)P(S)Prn2. An X-ray crystallographic investigation reveals a halide-bridged dimeric structure in which each bismuth atom is surrounded by an essentially octahedral arrangement of four chlorine [two terminal. Bi–Cl 2.500(5), 2.516(5), and two bridging, Bi–Cl 2.653(4). 3.015(5)Å] and two sulfur atoms [Bi–S 2.857(4), 2.973(4)Å]. Each of the two ligand molecules is involved in bidentate (S,S′) chelation to a bismuth atom to form a five-membered ring. Crystals are monoclinic, space group P21n, with a= 10.127(6), b= 16.057(6), c= 13.843(6)Å, β= 93.3(1)°, Z= 4. The reaction of BiCl3and tris(dimethylamino)phosphane selenide in acetonitrile gave the yellow crystalline salt [(Me2N)3PSeSeP(NMe2)3]2+[(BiCl4)2]n2n– as identified by a crystal structure determination. Formation of the unusual cation follows from air oxidation of the organophosphine selenide in the presence of BiCl3. The Se–Se bond distance is 2.309(5)Å and the torsion angle P–Se–Se–P is –112.4(4)°. For the anion, linkage of dimeric (BiCl4)2 units via further halide bridging results in an infinite chain structure of edge-shared octahedra. Crystals are triclinic, space group P with a= 7.386(6), b= 12.813(8), c = 18.919(8)Å, α= 76.0(1 ), β= 78.9(1 ), γ= 73.2(1)° and Z= 2.